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Synthesis of Pyrrolizidine, Indolizidine, and Quinolizidine Derivatives Using Ruthenium‐Catalyzed Ring‐Opening Metathesis and Ring‐Closing Metathesis of Cycloalkene‐ynes
Author(s) -
Wakamatsu Hideaki,
Sato Yoshihiro,
Fujita Reiko,
Mori Miwako
Publication year - 2007
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.200600539
Subject(s) - chemistry , ruthenium , metathesis , alkyne , enyne metathesis , ring opening metathesis polymerisation , catalysis , heptene , medicinal chemistry , organic chemistry , polymerization , polymer
Ring‐opening metathesis and ring‐closing metathesis (ROM‐RCM) of a cyclopentene‐yne having an ester moiety was demonstrated using first‐ and second‐generation Grubbs’ catalysts. When the reaction of cycloalkene‐yne was carried out in the presence of 5 mol % of a ruthenium carbene complex under an ethylene atmosphere at room temperature, ROM‐RCM proceeded smoothly to give a pyrrolidine derivative in good yield, which could be converted to a pyrrolizidine derivative. Furthermore, ROM‐RCM of azabicyclo[2.2.1]heptene‐ynes using the second‐generation Grubbs’ catalyst was investigated. When an azabicycloheptene derivative was exposed to a catalytic amount of a ruthenium carbene complex, pyrrolizidine and indolizidine derivatives were obtained in good yields. The distribution of these products depends on the substituents on the alkyne. When azabicyclo[2.2.1]heptene‐ynes bearing large substituents on the alkyne were treated with ruthenium catalyst 1b , a pyrrolizidine derivative was obtained as the major product. ROM‐RCM of azabicyclo[2.2.2]octene‐ynes with 1b afforded quinolizidine derivative 20 , although the yield was moderate.